Nitrogen-containing compounds

ABSTRACT

Compounds of the formula A--X--N +--N   -     n , wherein A is a linking group, X is an O--CO-- or --SO 2  -- group and n is at least 2, are prepared from the corresponding N&#39;,N&#39;-disubstituted hydrazides by quaternisation and treatment with alkali or reaction with an alkylene epoxide or from the corresponding compound wherein n = 1 and A is a polymerisable group by polymerisation. The compounds are unstable to heat and may be used as cross-linking agents for polymers or as chain-extending agents, bonding agents or adhesives.

This invention relates to nitrogen-containing compounds and moreparticularly to ammonioamidates containing two or more oxyformamidate orsulphonamidate groups.

According to the invention there are provided ammonio amidates of theformula ##STR1## WHEREIN A is a linking group to which the groups X areattached at alkyl, cycloalkyl or aryl carbon atoms, X is a group of theformula --O--CO-- or --SO₂ --, n is an integer of value at least 2, andR¹, R² and R³, which may be the same or different, are each anoptionally substituted alkyl, alkenyl, cycloalkyl or aralkyl group or R¹and R² together with the nitrogen atom joining them form a heterocyclicring or R¹, R² and R³ together with the nitrogen atom joining them formone or two heterocyclic rings.

As linking groups represented by A there may be mentioned alkylenegroups such as ethylene, 1,2- and 1,3-propylene, tetramethylene,hexamethylene, decamethylene, and dodecamethylene, cycloalkylene such as1,4-cyclohexylene, arylene such as m- and p-phenylene, groups derivedfrom combinations of the foregoing groups such asmethylene-bis-4-phenyl-, 2,2-propylene-bis-4-phenyl-, m- and p-xylylene,groups derived from one or more of the foregoing groups linked byheteroatoms or groups containing hetero atoms, such as1,4-phenylene-bis-oxyethyl-, from polyalkyleneoxides such aspolyethylene oxides, condensates of alkylene oxides with glycols andother compounds containing two or more hydroxyl groups such as glycerol,1,4-phenylene-bis-carbonyloxyethyl-, unsaturated polyvalent groupingsuch as may be derived from pentaerythritol dialkyl ether, and polymericchains to which the groups X are attached directly or through pendantgroups, as for example in addition polymers and copolymers of esters ofacrylic or methacrylic acids in which the group X is attached to thealkyl esterifying group.

As optionally substituted groups which may be represented by R¹, R² orR³ there may be mentioned alkyl groups preferably containing from 1 to 4carbon atoms such as ethyl, n and isopropyl, n-butyl, and especiallymethyl, but also n-octyl, n-decyl, n-dodecyl and n-octadecyl, cycloalkylgroups such as cyclohexyl, alkenyl groups such as allyl, aralkyl groupssuch as benzyl and β-phenylethyl, and substituted derivatives of thesesuch as β-hydroxyethyl, β-hydroxypropyl, β-methoxyethyl, β-cyanoethyl,β, γ-dihydroxypropyl and β-hydroxyoctyl. Any one of the groups R¹, R² orR³ may be joined to the same group in a second ammonioamidate residue toform an optionally substituted hydrocarbyl linking group such as analkylene group. The value of n is preferably 2.

As heterocyclic rings which may be represented by R¹ and R² and thenitrogen atom there may be mentioned morpholino, piperidino,pyrrolidino, piperazino and hexamethylene imine, and as heterocyclicrings which may be represented by R¹, R², R³ and the nitrogen atom theremay be mentioned pyridinium, picolinium, quinolinium, dipyridylium,1,4-bis-azonia-bicyclo[2,2,2]-octane, quinuclidinium and substitutedderivatives of these such as carboxypyridinium groups.

As specific examples of ammonioamidates of the invention there arementioned N,N'-bis(trimethylammonio)decamethylenebis-(oxyformamidate),N,N'-di-(1-pyridinio)propylene-2,2-bis-(4-phenoxyformamidate),N,N'-di-(1-pyridinio)methylenebis-(4-phenylsulphonamidate),N,N'-bis-(trimethylammonio)oxybis-(4-phenylsulphonamidate) andN,N'-bis-(4-methyl-4 -morpholinio)hexamethylenebis(oxyformamidate).

According to the invention there is also provided a process for themanufacture of ammonioamidates of the invention which comprises reactinga hydrazide of the formula ##STR2## wherein A, X, R¹, R², R³ and n havethe meanings given hereinbefore and M is an anion, with a basiccompound.

As basic compounds there may be mentioned for example alkalis such asalkali metal hydroxides, e.g. sodium and potassium hydroxides, alkalimetal carbonates such as sodium and potassium carbonates, alkali metalbicarbonates and anion exchange resins in the hydroxide form.

The process of the invention is conventionally carried out by stirringthe hydrazide and basic compound, preferably used in excess of up to100%, in a solvent such as a lower alcohol, e.g. ethanol. Reactiontemperatures between room temperatures and 100° C may be used, thepreferred temperature in each case depending upon the circumstances,such as the basis compound being used. The ammonioamidate may usually beisolated by removal of inorganic materials, for example by precipitationwith ethyl ether, and evaporation preferably under reduced pressure.

The hydrazides used in the process of the invention may be prepared fromthe corresponding compounds of the formula A--X-halogen)_(n), thehalogen being preferably chlorine, by reaction with a hydrazine of theformula NH₂ --NR¹ R² to give a hydrazide derivative of the formulaA--X--NH--NR¹ R²)_(n) followed by quaternisation with an alkylatingagent of the formula R³ M wherein M is an anion forming group, such aschlorine, bromine or iodine p-toluenesulphonate, or methosulphate. Themethod cannot be used when R¹, R² and R³ together with the nitrogen atomform one or two heterocyclic rings.

Alternatively the hydrazide may be obtained by reaction of the compoundof the formula A--X-halogen)_(n) with a quaternary hydrazine of theformula [NH₂ -- NHR¹ R² R³ ]_(x) M^(x) ⁻ wherein M is an anion forminggroup of functionality x, with a basic compound. This reaction and theconversion of the hydrazide into an ammonioamidate may be carried out inone state, and this represents a further feature of the invention. Thismethod is suitable for the preparation of any of the ammonioamidates ofthe invention.

An alternative process, suitable for the manufacture of ammonioamidatesof the invention wherein R³ is a β-hydroxyalkyl group, comprisesreacting the hydrazine derivative of the formula A--X--NH--NR¹ R²)_(n)with an epoxide such as ethylene or propylene oxide. The process may becarried out in a solvent such as tert.-butanol at a temperaturepreferably between 20° C and 150° C.

Alternatively the epoxide may be first reacted with a hydrazine of theformula H₂ N -- NR¹ R² either in the absence of solvent or in an aproticpolar solvent, such as ethylene glycol dimethyl ether and the reactionproduct treated with a compound of formula A--X-halogen)_(n), theammonioamidates wherein R³ is a β-hydroxyalkyl group being obtained upontreatment with basic compounds in the manner described above.

The hydrazides used in the process of the invention may also be preparedby alkylation of hydrazines of the formula A--X--NH--NH₂)_(n)

or A--X--NH--NHR¹)_(n) with alkylating agents such as R² M. Such methodare only suitable for the preparation of ammonioamidates wherein R¹, R²and R³ are the same or R² and R³ are the same respectively.

The ammonioamidates of the invention wherein A is a chain of an additionpolymer may also be obtained from the polymerisable unsaturatedammonioamidates described in our copending U.S. Pat. application Ser.No. 524,949 by polymerisation or by copolymerisation with otherpolymerisable unsaturated compounds, and this represents a furtherfeature of the invention.

Suitable polymerisable ammonioamidates are for exampleN-trimethylammonio-β-acryloyloxyethoxyformamidate,N-trimethylammonio-β-methacryloyloxyethoxyformamidate,N-trimethylammonio-β-methacryloyloxypropoxyformamidate andN-(4-methyl-4-morpholinio)-β-acryloyloxyethoxyformamidate.

Suitable copolymerisable unsaturated compounds are butyl acrylate,methoxypolyethyleneoxy acrylate, methyl acrylate, methyl methacrylate,β-dialkylaminoethyl acrylates, acrylamides, and vinyl pyrrolidone.

The polymerisation or copolymerisation may for example be carried out ina solvent such as carbon tetrachloride, benzene, toluene or ethylenedichloride using a polymerisation catalyst such asα,α'-azodiisobutyronitrile, or in aqueous medium using a catalyst systemsuch as potassium persulphate and potassium metabisulphite in presenceof a surfactant such as sodium dodecylbenzenesulphonate.

The ammonioamidates of the invention are solid compounds, soluble inwater except in those cases wherein the group A is devoid of watersolubilising groups and constitutes a major part of the molecule of theammonioamidate.

The ammonioamidates of the invention may be used as cross-linking agentsfor polymers, as chain extending agents for e.g. polyepoxides and otherpolyfunctional compounds, as bonding agents and adhesives for use withpolymers or other materials, and as coating agents. As polymers whichmay be cross-linked there may be mentioned natural rubber, syntheticrubbers such as styrenebutadiene, acrylonitrile-butadiene,ethylene-propylene rubbers, stero-regular polyisoprene, high or lowdensity polyethylene, polypropylene, nylons, polyurethanes etc. Any ofthe above polymers for example styrene-butadiene rubber may be bonded tothe same polymer, or a different polymer as for example stereo-regularpolyisoprene, or to other materials such as polyethylene terephthalate,nylon-6, nylon-6,6, rayon and metal substrates such as copper, brass andsteel, by means of the ammonioamidates of the invention.

The ammonioamidates may be incorporated into the polymer by for exampleblending with the polymer in any conventional manner, such as on atwo-roll mill, this type of procedure being especially suitable when theammonioamidate is to be used as a cross-linking agent and must bepresent throughout the bulk of the polymer. The polymer is thereaftershaped, for example in a mould, and heated to a temperature above 50° C,and preferably between 100° C and 250° C, to bring about cross-linking.The cross-linking may also be brought about by exposure to ultra-violetlight, but usually this will only bring about reaction at the surfaceexposed to the light.

For use as a bonding agent or adhesive, in which cases application ofthe ammonioamidate only at the surfaces of the polymer is usuallynecessary, it is generally more convenient and economical to treat thepolymer in shaped form, e.g. in filament, yarn, fabric, sheet or massiveform, with a solution of the ammonioamidate in, for example, water, andthen heat the treated polymer to drive off the water or solvent, bringthe surfaces to be bonded, e.g. polyester cord and rubber, into contact,and then heat more strongly to effect bonding. An auxiliary bondingagent such as an epoxy resin and resorcinol/formaldehyde reactionproduct may also be present to aid adhesion. Ammonioamidates where A isan unsaturated polyvalent grouping are particularly useful for polyesterto rubber bonding.

A similar procedure may be adopted to provide surfaces with coatingsexcept that in this case contacting of the surfaces is omitted. Exposureto ultra-violet light may in these cases be used satisfactorily as analternative to heating.

The ammonioamidates of the invention may also be used for any of thepurposes for which the monofunctional ammonioamidates of our copendingU.S. Pat. application Ser. No. 524,949 are used, the group A beingselected to suit the proposed application. For example coatings may beapplied which will confer water-repellency (A contains long chain alkylor fluoroalkyl groups or silicone polymer residues) or antistatic andantisoil properties (A contains polyalkylene oxide groups), or thepolymer may be provided with a coloured coating (A contains a dyestuffresidue), a protective coating against oxidation (A contains arylamineor phenolic residues) or coatings protective against fungal or bacterialattack (A contains bacterostatic or fungistatic groups).

The ammonioamidates in which A contains long chain alkyl groups may alsohave surfactant properties, and the ammonioamidates in general areaccelerators for the sulphur vulcanisation of rubber, and catalysts forthe formation of polyurethanes from polyisocyanates and polyhydroxyliccompounds and other base-catalysed reactions.

The uses of the ammonioamidates as listed hereinbefore provide furtherfeatures of the invention.

The invention is illustrated but not limited by the following Examplesin which all parts and percentages are by weight unless otherwisestated.

EXAMPLE 1

Phosgene gas (100 parts) was added to a suspension of2,2-bis-(4'-hydroxyphenyl) propane (114 parts; 0.5 mole) inmonochlorobenzene (450 parts at 0°-5° C, followed by a solution ofN,N-dimethylaniline (121 parts; 1.0 mole) in monochlorobenzene (150parts) added dropwise over 1 hour at 5°-10° C. The reaction temperaturewas raised to 40°-45° C for 2 hours after which time excess phosgene wasblown off with a stream of dry nitrogen. The reaction mixture was washedby shaking with water (2 × 250 parts), N-hydrochloric acid (250 parts),and water (250 parts) and dried over anhydrous magnesium sulphate. Themixture was filtered and the filtrate evaporated to dryness underreduced pressure to give 2,2-bis-(4'-chlorocarbonyloxyphenyl) propane(176 parts), m.p. 75° C.

A solution of the above chloroformate (53.3 parts; 0.15 mole) inchloroform (250 parts) was added dropwise over 30 minutes to a solutionof N,N-dimethylhydrazine (18 parts; 0.3 mole) in chloroform (50 parts)at 30°-35° C. The reaction mixture was stirred for 12 hours and thenwashed with water (3 × 250 parts) and dried over anhydrous magnesiumsulphate. The mixture was filtered and the filtrate evaporated todryness under reduced pressure to give2,2-bis(4-N,N-dimethylhydrazinocarbonyloxyphenyl) propane (49 parts)m.p. 70° C.

A mixture of the above bis-hydrazide (28 parts) and methyliodide (150parts) was heated under reflux for 24 hours. A yellow solid which formedwas filtered off, washed with diethyl ether and dried in vacuo to givethe diiodide (38 parts), m.p. 114°-115° C.

A mixture of the above diiodide (20.4 parts; 0.03 mole), ethyl alcohol(90 parts) and potassium carbonate (12.4 parts; 0.09 mol) was stirred at40°-45° C for 12 hours. The reaction mixture was filtered to removepotassium carbonate/bicarbonate and the filtrate diluted with diethylether (90 parts) to precipitate potassium iodide. The mixture wasfiltered and the filtrate evaporated to dryness under reduced pressureat 40° C. The solid was dried to constant weight under high vacuum overphosphorous pentoxide to give N,N-bis (trimethylammonio)propylene-2,2-bis (4-phenoxyformamidate) as a white solid (11.1 parts), m.p. 75°C. Infra red spectrum of the product showed a characteristic carbonylpeak at 1665 cm.sup.⁻¹.

EXAMPLE 2

Resorcinol (82.5 parts) was treated with phosgene (150 parts) in thepresence of N,N-dimethylaniline (181.5 parts) in monochlorobenzene (500parts) by the procedure described in Example 1 to give 1,3-bis(chlorocarbonyloxy)benzene (148 parts), b.p. 114° C/1.5 mm, m.p. 46°C.

A solution of 1,3 -bis(chlorocarbonyloxy)benzene (35.25 parts) intoluene (35 parts) was added dropwise over 30 minutes to a solution ofN,N-dimethylhydrazine (36 parts) in toluene (35 parts) at 25°-30° C. Thereaction mixture was stirred for 48 hours at 25° C and then filtered.The filter cake was extracted with chloroform (600 parts) at 45° C andthe mixture shaken with water (2 × 200 parts). The chloroform layer wasseparated and dried over anhydrous magnesium sulphate, filtered andevaporated to dryness under reduced pressure to give1,3-bis(N,N-dimethylhydrazinocarbonyloxy)benzene as a crystalline solid(41 parts), m.p. 134°-140° C.

A mixture of the above hydrazide (35.2 parts), methyl iodide (100 parts)and methanol (40 parts) was heated under reflux for 18 hours. Thereaction mixture separated into two layers and the upper layer wasseparated and evaporated to constant weight at 40° C/15 mm pressure togive the bis-trimethylammonium iodide as a clear, viscous oil (54parts). Found: C 30.0; H 4.7; N 9.8; I 41.0%; C₁₄ H₂₄ N₂ O₄ I₂ requiresC 29.7; H 4.2; N 9.9; I 44.9%.

A mixture of the above quaternary ammonium iodide (56 parts), ethylalcohol (150 parts) and potassium carbonate (41.4 parts) was stirredunder reflux for 12 hours after which time the mixture was filtered.Diethyl ether (150 parts) was then added to the filtrate followed by DY3carbon (2 parts). The mixture was shaken and filtered and solventsremoved at 35° C and 15 mm. pressure to give N,N'-bis(trimethylammonio)phenylene- 1,3 -bis(oxyformamidate), ahydroscopic, grey solid (24 parts), m.p. 56° C. Infrared spectrum showeda characteristic carbonyl peak at 1670 cm.sup.⁻¹.

EXAMPLE 3

1,4-Bis-(β-hydroxyethoxy)benzene (29.7 parts; 0.15 mole) was suspendedin methylene dichloride (700 parts) and the mixture added in portions(100 parts) to a stirred solution of phosgene (75 parts; 0.75 mole) inmethylene dichloride (50 parts) below 10° C. The temperature was raisedto 25° C and the reaction mixture stirred for 24 hours. More phosgene(50 parts) was added and the reaction stirred for further 12 hours at30° C and then for 8 hours at 35° C to form a clear solution. Excessphosgene was then blown off with a stream of dry nitrogen and thesolvent removed at 40° C and reduced pressure to give the correspondingbis-chloroformate (46 parts), m.p. 69° C. Found: Hydrolysable chloride21.1%; C₁₂ H₁₂ Cl₂ O₆ requires Cl 21.4%.

The above bis-chloroformate (32.3 parts; 0.1 mole) was reacted withN,N-dimethylhydrazine (24 parts; 0.4 mole) in toluene (100 parts)according to the method described in Example 2 to give thebis-N,N-dimethylhydrazide as a white solid (35 parts), m.p. 180° C.

A mixture of the above bis-N,N-dimethylhydrazide (35 parts), methyliodide (100 parts) and methanol (15 parts) was heated under reflux for18 hours, during which time a yellow solid formed. The solid wasfiltered off, washed with ether (100 parts) and dried in vacuo to givethe corresponding bis-N,N,N-trimethylhydrazinium iodide (54 parts), m.p.150° C.

A mixture of the above iodide (6.5 parts; 0.01 mole), ethyl alcohol (30parts) and potassium carbonate (4.2 parts; 0.03 mole) was stirred underreflux for 12 hours. Potassium carbonate and bicarbonate were filteredoff and the filtrate diluted with diethyl ether (30 parts) toprecipitate potassium iodide. The mixture was filtered and the filtratesevaporated to constant weight at 40° C under reduced pressure to giveN,N' -bis(trimethylammonio)phenylene- 1,4 -bis(oxyethoxyformamidate) asa hydroscopic, white solid (2.7 parts) m.p. 55° C. The infra redspectrum showed a characteristic carbonyl band at 1640 cm.sup.⁻¹.

EXAMPLE 4

The bis-chloroformate (9.5 parts), obtained frombis-β-hydroxyethylterephthalate by the procedure of Example 3, wasreacted with N,N-dimethylhydrazine (6 parts) in methylene dichloride (60parts) at room temperature to give the bis-N,N-dimethylhydrazide (11parts), m.p. 158°-160° C.

Quaternisation with methyl iodide at room temperature gave thebis-N,N,N-trimethylhydrazinium iodide, m.p. 132°-134° C. Treatment withaqueous (8N) potassium carbonate gaveN,N'-bis-(trimethylammonio)terephthaloyloxy-bis(ethoxyformamidate), m.p.180° C (decomp.). The infra red spectrum showed a characteristiccarbonyl band at 1630-1660 cm.sup.⁻¹.

EXAMPLE 5

Hexane-1,6-diol (236 parts; 2.0 mole) in methylene dichloride (1,800parts) and chloroform (250 parts) was reacted with phosgene (600 parts)at 5°-15° C for 18 hours essentially using the method described inExample 3, to give 1,6-hexamethylene dichloroformate (417 parts), b.p.125° C/1.5 mm.

1,6-Hexamethylene dichloroformate (364.5 parts; 1.5 mol) was reactedwith N,N-dimethylhydrazine (360 parts; 6.0 mole) in toluene (800 parts)according to the method described in Example 2 to give the correspondingbis-N,N-dimethylhydrazide (435 parts), m.p. 94° C. Found: C 49.7; H8.96; N 19.3%; C₁₂ H₂₆ N₄ O₄ requires C 49.9; H 8.9; N 18.6%.

The above bis-hydrazide (290 parts; 1.0 mole), methanol (50 parts) andmethyl iodide (300 parts) were heated together under reflux for 1 hour,after which time the solid was filtered off, washed with ether and driedin vacuo to give the bis-N,N,N-trimethylhydrazinium iodide (564 parts),m.p. 165° C.

The above bis-quaternary ammonium iodide (517 parts; 0.9 mole) in ethylalcohol (1000 parts) was treated with 1N alcoholic potassium hydroxide(1800 parts; 1.8 mole). Diethyl ether (1000 parts) was then added, thereaction mixture filtered, the filtrates were evaporated to drynessunder reduced pressure at 40° C, and the residue extracted withisopropanol (2000 parts) at 0° C. The isopropanol extract was filteredand then evaporated to dryness under reduced pressure at 40° C to giveN,N'-bis(trimethylammonio)hexamethylene- 1,6-bis(oxyformamidate) (119parts), m.p. 146° C. Found: N 17.2%; C₁₄ H₃₀ N₄ O₄ requires N 17.6%.Infra red spectrum showed a characteristic carbonyl peak at 1625cm.sup.⁻¹.

A similar product, N,N' -bis(ethyldimethylammonio)hexamethylene-1,6-bis(oxyformamidate) was obtained by using ethyl iodide as thequaternising agent instead of methyl iodide.

EXAMPLE 6

Butane-1,4-diol (270 parts; 3.0 mole) in methylene dichloride (800parts) and chloroform (150 parts) was reacted with phosgene (800 parts;8.0 mole) at 5°-15° C for 6 hours essentially using the method describedin Example 3 to give butane-1,4-dichloroformate (612 parts), b.p. 89°C/1.0 mm. Found: Cl 33.8%; C₆ H₈ O₄ Cl₂ requires Cl 33.0%.

The butane-dichloroformate (215 parts; 1.0 mole) was then reacted withN,N-dimethylhydrazine (240 parts; 4.0 mole) in toluene (1000 parts)according to the method described in Example 2 to give the correspondingbis-N,N-dimethylhydrazide (205 parts), m.p. 126° C. Found: C 46.1; H8.1; N 20.6%; C₁₀ H₂₂ N₄ O₄ requires C 45.8; H 8.4; N 21.4%.

The above bis-hydrazide (183.4 parts) was reacted with methyl iodide(190 parts) in methanol (50 parts) at 40° C for 3 hours and the solidformed dried to constant weight in vacuo to give thebis-N,N,N-trimethylhydrazinium iodide (380 parts), m.p. 140° C. Found: N9.5; I 44%; C₁₂ H₂₈ N₄ O₄ I₂ requires N 10.3; I 46.5%.

The above quaternary ammonium iodide (380 parts) in ethyl alcohol (1000parts) was treated with 1N alcoholic potassium hydroxide (1400 parts)essentially using the method described in Example 5 to give N,N'-bis(trimethylammonio)tetramethylene- 1,4 -bis(oxyformamidate) (130parts).

Alternatively, the above bis-N,N-dimethylhydrazide (26.2 parts; 0.1mole) was reacted with dimethyl sulphate (30 parts) in acetone (50parts) at 50° C for 2 hours, after which time the reaction mixture wasallowed to cool to 25° C. A white solid which separated was filteredoff, washed with acetone (10 parts) and dried to constant weight invacuo to give the bis-N,N,N-trimethylhydrazinium methosulphate (41parts), m.p. 125° C.

The above bis-quaternary ammonium methosulphate (40 parts) was treatedwith potassium carbonate (55.2 parts) in ethyl alcohol (250 parts) for36 hours, according to the method described in Example 2, to give the-bis(trimethylammonio-oxyformamidate) (24.3 parts), m.p. 165° C. Infrared spectrum shows a characteristic carbonyl peak at 1620 cm.sup.⁻¹.

EXAMPLE 7

Diethylene glycol (138 parts) was added dropwise to a solution ofphosgene (300 parts) in a methylene dichloride (200 parts) at 0°-5° Cduring 1 hour. The reaction mixture was warmed to 25° C during 3 hoursand then excess phosgene was blown off with a stream of dry nitrogen.The solvent was removed at 40° C under reduced pressure and the residuedistilled under nitrogen at reduced pressure to give thediethylether-bis-chloroformate (220 parts), b.p. 107° C at 0.75 mm.

The diethylether-bis-chloroformate (57.7 parts) was added dropwise to asolution of N,N-dimethylhydrazine (160 parts) in toluene (300 parts)over 1 hour at 30° C and the reaction mixture stirred for 12 hours. Awhite solid was filtered off, dissolved in chloroform (500 parts) andthe solution was washed with water, dried over magnesium sulphate,filtered and evaporated to dryness at 40° C under reduced pressure togive the bis-hydrazide (45 parts) m.p. 112° C. Found: C 42.8; H 8.2; N18.1%; C 10 H 22 N 405 requires C 42.4; H 7.9; N 20.1%.

The bis-hydrazide (27.8 parts) dissolved in acetone (150 parts) wasquaternised with dimethyl sulphate (30 parts) to give the bis-quaternarysulphate (48 parts), m.p. 122° C. Treatment with potassium carbonate(55.2 parts) in ethyl alcohol (250 parts) followed by filtration andevaporation of the filtrate under reduced pressure gave N,N'-bis(trimethylammonio)diethylether-bis(oyformamidate) (29 parts), m.p.134° C. Infra red spectrum showed a characteristic carbonyl peak at 1640cm.sup.⁻¹.

EXAMPLE 8

Triethylene glycol (150 parts) in methylene dichloride (200 parts) wasreacted with phosgene (1300 parts) at 0° - 5° C over 2 hours, using themethod described in Example 3, to give the bis-chloroformate (268parts), b.p. 145° C/1.5 mm.

The bis-chloroformate (68.7 parts) in toluene (300 parts) was reactedwith N,N-dimethylhydrazine (60 parts), followed by quaternisation of thebis-hydrazide (32.2 parts) in acetone (150 parts) with dimethylsulphate(30 parts) and treatment of the bis-quaternary salt with potassiumcarbonate according to the procedure described in Example 7 to giveN,N-bis(trimethylammonio)diethoxyethane-bis-(oxyformamidate) as a paleyellow oil (26 parts). Infra red spectrum showed a characteristiccarbonyl peak at 1640 cm.sup.⁻¹.

EXAMPLE 9

Polyethylene glycol of molecular weight approximately 300 in methylenechloride (200 parts) was reacted with phosgene (300 parts) at 0°-10° Cover 2 hours using the method described in Example 3, to give thebis-chloroformate (411 parts).

A paste of the bis-chloroformate (137.5 parts) was then reacted withN,N-dimethylhydrazine (72 parts) followed by quaternisation of thebis-hydrazide with dimethyl sulphate and treatment with potassiumcarbonate according to the procedure described in Example 7, to giveN,N'-bis(trimethylammonio)polyethoxyethane-bis(oxyformamidate) (41parts). Infra red spectrum showed a characteristic carbonyl peak at 1640cm.sup.⁻¹.

EXAMPLE 10

1,10-Decamethylene glycol (52.2 parts; 0.3 mole) in methylene dichloride(800 parts) was reacted with phosgene (100 parts) at 20°-25° C for 24hours essentially using the method described in Example 3, to give1,10-decamethylene glycol dichloroformate (90 parts). Found: Cl 24.8%;C₁₂ H₂₀ O₄ Cl₂ requires Cl 23.7%.

1,10-Decamethylene glycol dichloroformate (44.9 parts; 0.15 mole) wasthen reacted with N,N-dimethylhydrazine (36 parts; 0.6 mole) in toluene(250 parts) according to the method described in Example 2, to give thecorresponding bis-hydrazide (47 parts), m.p. 106° C.

The above bis-hydrazide (43.2 parts), methanol (20 parts) and methyliodide (100 parts) were heated together under reflux for 24 hours, afterwhich time the solvent was removed at 40° C under reduced pressure togive the derived bis-N,N,N-trimethylhydrazinium iodide (79 parts), m.p.125° C.

The above quaternary ammonium iodide (12.6 parts) was treated withpotassium carbonate (8.4 parts) in ethyl alcohol (60 parts) according tothe method described in Example 2 to giveN,N'-bis(trimethylammonio)decamethylene-bis(oxyformamidate) as a whitesolid (6.7 parts), m.p. 115°-117° C. Found: C 57.7; H 9.8; N 14.0%; C₁₈H₃₈ N₄ O₄ requires C 57.7; H 10.2; N 15.0%. Infra red spectrum showed acharacteristic carbonyl band at 1640 cm.sup.⁻¹.

EXAMPLE 11

Polyethylene glycol of molecular weight approximately 1000 (250 parts)was heated to 40° C and phosgene (55 parts) bubbled in with stirring atthe rate of about 1.0 part per minute. The reaction mixture was stirredat 40° C for 3 hours and excess phosgene removed under reduced pressureusing nitrogen, to give the bis-chloroformate (281 parts).

A part of the bis-chloroformate (112.5 parts) was then reacted withN,N-dimethylhydrazine (25 parts), followed by quaternisation of thebis-hydrazide with methyl iodide and treatment with potassium carbonateaccording to the procedure described in Example 10 to giveN,N'-bis(trimethylammonio)polyethanoxy-bis(oxyformamidate) as a white,waxy solid (120 parts).

EXAMPLE 12

Oxyethylated glycerol (28.25 parts) having a molecular weight of 1130was heated to 40°C and phosgene (8.3 parts) was bubbled into the liquidwith stirring at the rate of about 0.08 part per minute. The reactionmixture was stirred at 40° C for a further 3 hours and excess phosgenethen removed under reduced pressure with a stream of nitrogen. Thechloroformate so obtained was then reacted with excessN,N-dimethylhydrazine in chloroform followed by quaternisation withmethyl iodide and treatment with potassium carbonate as described inExample 1, to give a tristrimethylammonioformamidate having an averageof about 24 ethylene oxide units per molecule.

EXAMPLE 13

Diphenyl ether 4,4'-disulphonyl chloride was dissolved in toluene (200parts) and the solution cooled to 10° C. N,N-dimethylhydrazine (36parts; 0.6 mole) was then added dropwise over 30 minutes at 10°-15° C,after which the mixture was stirred at room temperature for 12 hours.The solid was filtered off and dissolved in ethyl acetate (1000 parts)at 90° C. The solution was washed with water (2 × 250 parts), dried overanhydrous magnesium sulphate, and evaporated at 45° C under reducedpressure to give the bis-sulphonyl hydrazide as a white solid (50parts), m.p. 132° C. Found: N 13.6; S 15.3%; C₁₆ H₂₂ O₅ S₂ N₄ requires N13.5; S 15.5%.

A mixture of the above N,N-dimethylhydrazide (52 parts), methanol (50parts) and methyl iodide (300 parts) was heated under reflux for 36hours, during which time a yellow solid formed. The solid was filteredoff, washed with diethyl ether and dried in vacuo to give4,4'-bis(N,N,N-trimethylhydrazinium sulphonyl)diphenylether diiodide (32parts), m.p. 132°-4° C.

The above quaternary iodide (6.9 parts; 0.01 mol) was dissolved in ethylalcohol (20 parts) and the solution treated with alcoholic potassiumhydroxide (20 parts; 0.02 mol). The reaction mixture was stirred at 25°C for 2 hours, followed by 1 hour at 60° C. The reaction mixture wasfiltered and the filtrate diluted with diethyl ether (40 parts) to forma white precipitate. The solid was filtered off and dried in adesiccator to give the bis-ammoniosulphonamidate as a white solid (3.5parts), m.p. 88° C. Found: C 49.1; H 6.0; N 12.9%; C₁₈ H₂₆ N₄ O₅ S₂requires C 48.8; H 5.9; N 12.7%. The infra red spectrum showedcharacteristic -NSO₂ - bands at 1265 and 1125 cm.sup.⁻¹.

EXAMPLE 14

Diphenylmethane-4,4'-disulphonyl chloride (54.7 parts; 0.15 mol) wasdissolved in toluene (300 parts) and the solution cooled to 10°-15° C;N,N-dimethylhydrazine (36 parts; 0.6 mol) was then added dropwise over 1hour at 10°-15° C, after which time the reaction mixture was stirred for16 hours at 250° C. The solid which separated was filtered off,dissolved in chloroform (500 parts), the solution washed with water (2 ×250 parts), dried over anhydrous magnesium sulphate and evaporated at40° C under reduced pressure to give the bis-sulphonyl hydrazide as awhite solid (52.5 parts), m.p. 100° C. Found: C 49.3; H 6.4; S 15.2%;C₁₇ H₂₄ O₄ N₄ S requires C 49.5; H 5.8; S 15.5%.

The above bis-hydrazide (51.5 parts) in methanol (100 parts) wasquaternised with methyl iodide (200 parts) using the method given inExample 2, to give the diiodide as a brownish solid (54 parts), m.p. 68°C.

A mixture of the above iodide (48 parts), ethyl alcohol (100 parts) andN alcoholic potassium hydroxide solution (138 parts) was stirred at 25°C for 12 hours and then filtered. Diethyl ether (225 parts) was addedthen to he filtrates to precipitate a yellow oil. The oil was separated,extracted with ethyl alcohol (75 parts), the solution filtered andevaporated to dryness under reduced pressure to leave thebis-ammoniosulphonamidate as a hydroscopic yellow solid (17 parts), m.p.62° C. Found: S 14.8%; C₁₉ H₂₈ N₄ O₄ S₂ requires S 14.5%. The infra redspectrum showed bands at 1250 and 1140 cm.sup.⁻¹.

EXAMPLE 15

N-trimethylammonio-β-acryloyloxyethoxyformamidate was prepared by theprocedure described in our copending U.S. Pat. application Ser. No.524,949, in which β-hydroxyethyl acrylate was reacted with phosgene inmethylene dichloride at 10° C, and then with N,N-dimethylhydrazine intoluene at 10°-20° C, followed by quaternisation with methyl iodide atroom temperature and treatment with potassium carbonate in ethanol at25°C.

N-trimethylammonio-β-acryloyloxyethoxyformamidate (15 parts) wasdissolved in carbon tetrachloride (15 parts) and stirred at 45°-50° Cunder nitrogen. A solution of α,α'-azodiisobutyronitrile (10.3 parts) incarbon tetrachloride was added over 4 hours at 45°-50° C during whichtime the solution thickened and eventually deposited a rubbery polymer.This was separated from the reaction liquors, washed with diethyl etherand dried in vacuo, to give a rubbery white polymer (12 parts) of theformula: ##STR3## where the average n is from 4 to 25 depending on hereaction temperatute and time.

Co-polymerisation of the N-trimethylammonio-β-acryloyloxyethoxyformamidate (1 mole) with butyl acrylate (5 moles) under similarconditions gave a white, rubbery copolymer of molecular weight about5000.

EXAMPLE 16

A solution of N-trimethylammonio-β-acryloyloxyethoxyformamidate (5parts) and sodium dodecylbenzene sulphonate (0.4 parts) in water (25parts) was treated dropwise under nitrogen with a solution of potassiummetabisulphite (0.3 parts) in water (10 parts) and potassium persulphate(0.3 parts) in water (2 parts) over 3 hours at 20°-25° C. The reactionmixture was stirred for a further 14 hours to give a cloudy, aqueousemulsion (43 parts) containing 11.6% polymeric ammonioamidate similar tothat prepared in the preceding Example 15.

Co-polymerization of methoxy-polyethylene glycol 350 acrylate,containing about 7.25 ethylene oxide units per molecule, (5 moles) withN-trimethylammonio-β-acryloyloxyethoxyformamidate (1 mole) by the aboveprocedure gave a water-soluble co-polymer.

EXAMPLE 17

Hydroxylamino-O-sulphonic acid (12.15 parts) was dissolved in water (100parts) and neutralised at below 20°C with a solution of potassiumhydroxide (6.02 parts) in water. Pyridine (40 parts) was then added andthe mixture heated at 70°-80° C for 3 hours, cooled and treated withanhydrous potassium carbonate (13.8 parts). After standing for 18 hoursat room temperature the mixture was evaporated to dryness at below 50°C, and the residue extracted several times with chloroform to a total of500 parts by volume. The chloroform extracts were filtered, combined andanhydrous potassium carbonate (20 parts) and2,2-bis(4-chlorocarbonyloxyphenyl)propane, prepared as described inExample 1 (17.7 parts) added. The mixture was allowed to stand at roomtemperature for 70 hours and stirred at 50°-60° C for 3 hours, thenfiltered and the chloroform evaporated to give a crude product (28parts).

Trituration with tetrahydrofuran gave a solid (4.75 parts) which wasrecrystallised from dioxan to give a product m.p. 152°-154° Cidentifiable by infra red, NMR and elementary analysis asN,N-di(1-pyridinio)pyopylene-2,2-bis(4-phenoxyformamidate).

EXAMPLE 18

Phosgene (100 parts) was passed into methylene dichloride (100 parts byvolume) at 0°-5° C, and a solution of hexane-1,6-diol (35.4 parts) inmethylene dichloride (750 parts by volume) was then added in severalportions at 5°-10° C allowing 30 minutes between each addition. Thereaction mixture was stirred for 18 hours warming to room temperature,then degasses with a nitrogen stream for 5 hours at room temperature.Methylene dichloride was removed under atmospheric pressure and theresidue stirred at room temperature under a pressure of 18 mm of mercuryfor 1 hour. Hexane-1,6-diol bis-chloroformate (65 parts) was obtained asa clear liquid.

To a suspension of 1-amino-pyridinium iodide (8.88 parts) suspended inethanol (250 parts by volume) were added concurrently molar alcoholicpotassium hydroxide (50 parts), and hexane-1,6-diol bis-chloroformate5.35 parts dissolved in 50 parts by volume of ethanol) at such a ratethat a purple colour was maintained in he reaction mixture. Afterstirring for 3 hours at room temperature the reaction mixture wasevaporated to dryness under partial vacuum, dissolved in 10% aqueoussodium carbonate (200 parts by volume) and the carbonate solutionextracted with methylene dichloride. The extracts were dried overanhydrous sodium sulphate, and the methylene dichloride distilled off,leaving an oil. This was recrystallised from dioxane to give a solid(2.75 parts), m.p. 122°-125° C. Elementary analysis and infra red andNMR spectra identified the product asN,N'-di(1-pyridinio)hexamethylenebis(oxyformamidate).

EXAMPLE 19

Butane-1,4-dichloroformate prepared according to the method described inExample 3 (32.2 parts; 0.15 mole) and reacted with 1-aminopyridiniumiodide (66.6 parts; 0.3 mole) and potassium hydroxide (33.6 parts; 0.6mole) in chloroform (700 parts), according to the method described inExample 18 to giveN,N'-di(1-pyridinio)tetramethylene-1,4-bis(oxyformamidate) (12 parts),m.p. 145° C. Found: N 16.5%; C₁₆ H₁₈ N₄ O₄ requires N 17.0%. Infra redspectrum showed a characteristic carbonyl peak at 1630 cm.sup.⁻¹.

This product was also prepared by the following procedure:-Butane-1,4-dichloroformate (215 parts), 1-aminopyridinium sulphate (286parts) potassium hydroxide (112 parts) and potassium carbonate (346parts), were stirred in a mixture of water (200 parts) and t-butanol(500 parts) at 10°-15° C over 2 hours. Ethyl alcohol (300 parts) wasthen added and the reaction mixture stirred for further 48 hours at 25°C. The reaction mixture was filtered to remove potassium sulphate andevaporated to dryness under reduced pressure. The residue was dissolvedin chloroform (1,000 parts), the solution treated with carbon, filtered,and evaporated to dryness at 45° C under reduced pressure to giveN,N'-di-(1-pyridinio) tetramethylene-1,4-bis(oxyformamidate) (180parts).

EXAMPLE 20

Decane-1,10-dichloroformate prepared according to the method describedin Example 10 (29.9 parts) was reacted with 1-amino-pyridinium sulphate(28.6 parts) and potassium carbonate (55.2 parts) in a mixture of water(50 parts) and t-butanol (150 parts) according to he method described inExample 19 to giveN,N'-di-(1-pyridinio)decamethylene-1,4-bis(oxyformamidate) (20 parts),m.p. 60° C. Infra red spectrum showed a characteristic carbonyl peak at1630 cm.sup.⁻¹.

EXAMPLE 21

Terephthaloyloxy-bis(ethoxychloroformate) prepared as in Example 4 (18.9parts) was dissolved in ethylacetate (150 parts) and added dropwise to aslurry of 1-aminopyridinium sulphate (14.3 parts) and potassiumcarbonate (27 parts) in a mixture of water (20 parts) and tert.-butanol(60 parts) over 30 minutes at 5°-10° C. The reaction mixture was thenstirred for 36 hours and filtered. The solid was washed with alcohol(200 parts) and the combined filtrates and washings evaporated todryness under reduced pressure. The residue was dissolved in chloroform,the solution treated with carbon, dried over magnesium sulphate,filtered and evaporated to dryness to give N,N'-bis(1-pyridinio)terephthaloyloxy-bis(ethoxyformamidate), m.p. 126° C. Found: C 58.3; H4.6; N 10.5%; C₂₅ H₂₂ N₄ O₈ requires C 58.3; H 4.5; N 11.3%.

EXAMPLE 22

1,4-Bis (β-chlorocarbonyloxyethoxy)benzene, prepared as described inExample 3, (145.5 parts) was reacted with a suspension of1-amino-pyridinium sulphate (109 parts); potassium hydroxide (42 parts)and potassium carbonate (151.8 parts) in a mixture of water (350 parts)and tert.-butanol (700 parts) at 10°-15° C for 2 hours. The reactionmixture was stirred for a further 3 hours at 15° C and 48 hours at 25°C. The reaction mixture was then evaporated to dryness under reducedpressure at 45° C and the residue slurried in water, (1400 parts), atroom temperature and in ethyl alcohol (1400 parts) at 60° C. The solidresidue was filtered off, washed with ethyl alcohol and dried in vacuoto give N,N'-bispyridinio-1,4 phenylene-bis(oxyethoxyformamidate) (122parts), m.p. 186° C. Infra red spectrum showed a characteristic carbonylbond at 1630 cm.sup.⁻¹.

EXAMPLE 23

The bis-chloroformate prepared from diethylene glycol according to themethod described in Example 10 (46.2 parts) was reacted with1-amino-pyridinium sulphate (57.2 parts) and potassium carbonate (108parts) in a mixture of water (80 parts) and tert.-butanol (250 parts) at10°-15° C over one-half hour, followed by 48 hours at 25° C. Thereaction mixture was filtered to remove potassium sulphate and thefiltrates evaporated to dryness at 45° C under reduced pressure. Thesolid was dissolved in chloroform (500 parts), the solution treated withcarbon, dried over magnesium sulfate, filtered and evaporated toconstant weight at 45° C under reduced pressure to give N,N'-di(1-pyridinio) diethylether-bis-(oxyformamidate) (55 parts). Infra redspectrum showed a characteristic carbonyl bond at 1635 cm.sup.⁻¹.

EXAMPLE 24

The bis-chloroformate prepared from triethylene glycol according to themethod described in Example 8 (27.5 parts) was reacted with1-aminopyridinium sulphate (42.9 parts), potassium carbonate (82.8parts) in water (60 parts) and tert.-butanol (200 parts) according tothe method described in Example 8 to give N,N'-di (1-pyridinio)diethanoxyethane-bis (oxyformamidate) (31 parts) as a pale brown solid,m.p. 110° C. Infra red spectrum showed a characteristic carbonyl bond at1640 cm.sup.⁻¹.

EXAMPLE 25

The bis-chloroformate of molecular weight approximately 540 preparedfrom polyethylene glycol according to the method described in Example 9(42.5 parts) was reacted with 1-aminopyridinium sulphate (28.6 parts),potassium carbonate (55.2 parts) in water (50 parts) and tert.-butanol(150 parts) according to the method described in Example 8 to giveN,N-bis-(pyridinio) polyethoxyethane-bis (oxyformamidate) (53 parts) asa pale yellow oil. Infra red spectrum showed a characteristic carbonylbond at 1640 cm.sup.⁻¹.

EXAMPLE 26

Hexane-1,6-diol-bis-chloroformate, prepared as described in Example 18(14.6 parts) was reacted with 1-amino-2,6-dimethyl pyridinium iodide (20parts) and potassium carbonate (22 parts) suspended in a mixture ofwater (100 parts) and t-butanol (200 parts) at 20°-25° C over 24 hours.the reaction mixture was evaporated to dryness and the residue wastreated with chloroform and filtered to remove inorganic salts. thefitrates were evaporated and the resulting brown oil recrystallised fromtetrahydrofuran to give N,N'-di(2,6-dimethyl-1-pyridinio) hexamethylenebis-(oxyformamidate) m.p. 170°-172° C.

Analysis found C = 63.4%; H = 7.8%; N = 13.8%

Calculated for C₂₂ H₃₀ O₄ N₄ ; H = 7.3%; N = 13.5%.

EXAMPLE 27

The 4-amino morpholine hydrochloride (55.4 parts) was added at 5° C.Sodium hydroxide (16 parts) dissolved in water (260 parts).hexan-1,6-diol-bis-chloroformate prepared as in Example 18, (26.7 parts)in 540 parts of chloroform was added at 0° C. The reaction mixture wasallowed to warm slowly to 20°-25° C, and was then evaporated to dryness.The residue was triturated with diethyl ether and then with water. Thewater insoluble material as filtered off and dried to give1,6-bis-(morpholin-4-ylaminocarbonyloxy) hexane (25.4 parts) m.p.197°-199° C which showed an infra red absorption at 1710 cm.sup.⁻¹.

1,6-Bis(morpholin-4-ylaminocarbonyloxy)hexane (26 parts) and neutraliseddimethyl sulphate (116 parts) were stirred together at 50°-55° C for 16days. The excess dimethyl sulphate was removed leaving the quaternaryhydrazinium compound as a viscous brown oil showing an absorption in theinfra red at 1750-1740 cm.sup.⁻¹. This was stirred with potassiumcarbonate (48.3 parts) and ethanol (500 parts) at 20°-25° C for 7 days.The reaction mixture was filtered and the filter-cake was washed with alittle ethanol. The filtrate and washings were evaporated to dryness toyield N,N'-bis(4-methylmorpholinio) hexamethylene-bis-oxyformamidate asa brown oil having a carbonyl absorption in the infra red at 1625cm.sup.⁻¹.

The ammonioamidate could be purified by dissolving in a little ethanoland adding oxalic acid dihydrate in ethanol to a pH of 3-4. The oxalatesalt precipitated almost immediately and was filtered off. Theammonio-amidate could be recovered by suspending the oxalate salt inwater and adding sodium hydroxide solution to a pH of 7 when a clearsolution was obtained. This was evaporated to dryness and the residuetriturated with ethanol and filtered. The filtrates were evaporated toyield the ammonioamidate m.p. 90° C.

Analysis found N = 12.7%

Calculated for C₁₈ H₃₄ O₆ N₄ N = 13.9%

EXAMPLE 28

The procedure of Example 27 was repeated replacing the hexane-1,6-diolbis-chloroformate by an equivalent ammount of1,4-bis-(β-chlorocarbonyoxyethoxy)benzene, prepared as described inExample 3. 1,4-Bis(morpholin-4-ylaminocarbonyloxyethoxy)benzene, m.p.219°-221° C, was obtained.

Quaternisation of this bishydrazide with dimethylsulphate andbasification of the resultant bis-hydrazinium methosulphate withpotassium carbonate in ethanol according to the method of Example 27 ledto the formation of N,N'-bis(4-methylmorpholino) 1,4-phenylenebis(oxyethoxyformamidate) as a light brown solid m.p. 127° C.

Analysis found N = 11.2%

Calculated for C₂₂ H₃₄ O₈ N₄ N = 11.6%.

EXAMPLE 29

1-Aminopyridinium sulphate (14.3 parts) was dissolved in water (40parts) and the solution was cooled to 10° C. Finely grounddiphenylether-4,4'-disulphonylchloride (18.4 parts) was added inportions and at the same time sodium hydroxide 8 parts in water (80parts) was added to maintain a pH of 12-13 in he reaction mixture. Afterthe additions the reaction mixture was allowed to warm to 20°-25° C over24 hours, stirred for 72 hours, and then filtered. The filter-cake wasdried and extracted with methylene chloride. Methylene chloride wasevaporated from the extracts to give a solid which was treated withethanol at reflux, cooled and again filtered to giveN,N'di(1-pyridinio)diphenylether-4,4' disulphon-amidate m.p. 229°-231°C.

Analysis Found: N = 11.4%, S = 13.6%,

Calculated for C₂₂ H₁₈ O₅ N₄ S₂ ; N = 11.6%; S = 13.3%.

EXAMPLE 30

To a suspension of 1-aminopyridinium iodide (22.2 parts) in ethanol (500parts by volume) were added concurrently molar alcoholic potassiumhydroxide (270 parts by volume) and diphenyl ether-4,4'-disulphonylchloride (36.7 parts) dissolved in chloroform (500 parts by volume). Themixture was stirred at room temperature for 48 hours, and thenevaporated to dryness under partial vacuum. The residue was dissolved inaqueous isopropanol, molar alcoholic potassium hydroxide added to pH11-12, and again evaporated to dryness. The residue (46 parts) wasextracted with methylene chloride in a Soxhlet extractor to yield 11.3parts of N,N'-di(1-pyridinio)diphenylether-4,4'-disulphonamidate,identical with the product obtained as described in Example 29.

EXAMPLE 31

In place of the diphenyl ether-4,4'-disulphonyl chloride of Example 26,diphenyl methane-4,4'-disulphonyl chloride was employed and theresulting N,N'-di(1-pyridinio)methylenebis(4-phenylsulphonamidate) wasobtained as a solid, m.p. 130°-140° C.

EXAMPLE 32

2 parts of an ammonioamidate, 1 part of an epoxy resin commerciallyavailable under the name Epon 812 and 0.112 parts of surfactant (sodiumdioctylsulphosuccinate) were added with stirring to 42 parts of water.Polyethylene terephthalate cord (3/1100) was passed through the aboveaqueous composition and then dried in an oven at 230° C for 45-60seconds. the treated cord was then passed through an emulsion comprisinga partly polymerised resorcinol/formaldehyde resin (16.2 parts), 25%aqueous sodium hydroxide (1.2 parts), 37% aqueous formaldehyde (11.8parts), 41% aqueous polyvinylpyridine/styrene butadiene copolymer latex(244 parts), 28% aqueous ammonia (11.3 parts) and water (297 parts). Thecord was then again dried in an oven at 230° C for 45-60 seconds.

A rubber mix was prepared from the following ingredients:

    ______________________________________                                        Natural rubber           100    parts                                         Zinc oxide               3.5    parts                                         Stearic acid             1.5    parts                                         General purpose furnace black                                                                          35     parts                                         Processing oil           3      parts                                         Sulphur                  2.5    parts                                         Benzthiazyl sulphencyclohexylamide                                                                     1      part                                          ______________________________________                                    

The treated cord was brought into contact with the rubber mix and thewhole vulcanised at 150° C for 40 minutes. The bond between the rubberand the cord was measured by determining the force necessary to pull thecord out of the rubber.

    ______________________________________                                        Ammonioamidate    Force to separate (kg)                                      ______________________________________                                        None              5.4                                                         Product of Example 5                                                                            7.9                                                         Product of Example 6                                                                            6.9                                                         Product of Example 18                                                                           9.5                                                         Product of Example 19                                                                           10.7                                                        Product of Example 22                                                                           11.3                                                        Product of Example 24                                                                           7.1                                                         ______________________________________                                    

EXAMPLE 33

The bis(trimethylammonio oxyformamidate) of Example 6 was mixed with tentimes its weight of a glycidyl ether of glycerol containingapproximately 2 glycidyl groups per molecule. The mixture was stable onstorage at room temperature. On heating at 180° C for 0.5 hours a tough,cured, rubbery film was obtained.

A similar film was obtained on heating at 180° C for 0.5 hours a mixtureof the bis(pyridinio oxyformamidate) of Example 18 and the glycidylether used above.

What we claim is:
 1. A compound of the formula ##EQU1## wherein A is adivalent radical selected from the class consisting of ##SPC1##--(CH₂)_(x) -- where x has a value 4 to 10 and -- CH₂ CH₂ --OCH₂ CH₂)_(m)OCH₂ CH₂ -- where m has the value 0 or 1 and each of R¹, R² and R³ islower alkyl.
 2. Ammonioamidates as claimed in claim 1 wherein each ofR¹, R² and R³ is a methyl group.